Spectrothermal studies of 1,10-phenanthroline complexes of Co(II), NI(II), Cu(II) and Cd(II) orotates

Article abstract of DOI:10.1007/s10973-005-7137-2

The 1,10-phenanthroline (phen) complexes of Co(II), Ni(II), Cu(II) and Cd(II) orotates were synthesized and characterized by elemental analysis, magnetic susceptibility, spectral methods (UV-vis and FTIR) and thermal analysis techniques (TG, DTG and DTA). The Co(II), Ni(II), Cu(II) and Cd(II) ions in diaquabis(1,10-phenanthroline)metal(II) diorotate octahedral complexes [M(H ₂O)₂(phen)₂](H₂Or) ₂?nH₂O (M=Co(II), n=2.25; Ni(II), n=3; Cu(II) and Cd(II), n=2) are coordinated by two aqua ligands and two moles of phen molecules as chelating ligands through their two nitrogen atoms. The monoanionic orotate behaves as a counter ion in the complexes. On the basis of the first DTG _max, the thermal stability of the hydrated complexes follows the order: Cd(II), 68°C

Full text of DOI:10.1007/s10973-005-7137-2

Journal of Thermal Analysis and Calorimetry, Vol. 86 (2006) 1, 211–216
SPECTROTHERMAL STUDIES OF 1,10-PHENANTHROLINE
COMPLEXES OF Co(II), Ni(II), Cu(II) AND Cd(II) OROTATES
1
O. Z. Yeîilel and H. Ölmez
*
2
1
Department of Chemistry, Faculty of Arts and Sciences, Eskiêehir, Osmangazi University, 26480 Eskiêehir, Turkey
2
Department of Chemistry, Faculty of Arts and Sciences, Ondokuz MayÏs University, 55139 Kurupelit, Samsun, Turkey
The 1,10-phenanthroline (phen) complexes of Co(II), Ni(II), Cu(II) and Cd(II) orotates were synthesized and characterized by
elemental analysis, magnetic susceptibility, spectral methods (UV-vis and FTIR) and thermal analysis techniques (TG, DTG and
DTA). The Co(II), Ni(II), Cu(II) and Cd(II) ions in diaquabis(1,10-phenanthroline)metal(II) diorotate octahedral complexes
[
M(H
two moles of phen molecules as chelating ligands through their two nitrogen atoms. The monoanionic orotate behaves as a counter
ion in the complexes. On the basis of the first DTGmax, the thermal stability of the hydrated complexes follows the order: Cd(II),
8°C<Ni(II), 74°C<Cu(II), 135°C<Co(II), 166°C in static air atmosphere.
2 2 2 2 2 2
O) (phen) ](H Or) ·nH O (M=Co(II), n=2.25; Ni(II), n=3; Cu(II) and Cd(II), n=2) are coordinated by two aqua ligands and
6
Keywords: orotic acid complexes, 1,10-phenanthroline complexes, spectrothermal analysis
Introduction
[Ni(HOr)(H O) ], [M(HOr)bipy(H O)] (M=Mn(II),
2 3 2
Co(II)) [19], [Co(HOr)(OH)(H O)(NH )] and
[Ni(HOr)(OH)(H O) (NH )] complexes [20] the
2
3 n
Orotic acid (1,2,3,6-tetrahydro-2,6-dioxo-4-pyrimidine-
carboxylic acid, vitamin B , H Or, Fig. 1) occupies a
2
2
3 n
13
3
orotate anion acts as a bridge between the metal ions
forming one-dimensional polymeric chains, its coordi-
nation sites being the carboxylate and the N(3) and O(4)
atoms. In the polymeric copper(II)-orotato complexes,
[Cu(HOr)(H O) ] , the molecules form chains in a way
unique position biologically by being the only effective
precursor in the biosynthesis of the pyrimidine based of
nucleic acids [1–3]. Metal orotates are also widely ap-
plied in medicine. Recent interest has focused on the
proposed biological carrier function of orotic acid and
the corresponding anionic species for metal ions, which
is held responsible for the obviously successful applica-
tion of metal orotates in curing syndromes associated
with a deficiency of a variety of metals such as calcium,
magnesium, zinc or iron [4, 5]. Besides biologically im-
portant, orotic acid is also an interesting ligand in coor-
dination chemistry. It may coordinate through the two
nitrogen atoms of the pyrimidine ring, the two carbonyl
oxygens and the carboxyl group. Although, the most po-
tential coordination sites are the deprotonated carboxyl
group and its adjacent nitrogen, when they coordinate to
metal ion, the complexation ability of the exocylic car-
bonyl oxygen is greatly enhanced [6]. Owing to the bio-
logical interest in orotic acid complexes, several investi-
gators have focused their attention on the coordinating
properties of the acid. It was found that, in neutral or
slightly acidic environment, it coordinates through the
carboxylate group while in basic surroundings it coordi-
nates through the carboxylate and the adjacent N(3)
2
2 n
that the carboxylate group acts as a bridge between the
metal ions and the orotato-group being tridentate [21].
In the present paper, the synthesis, spectroscopic
properties and thermal decomposition of the Co(II),
Ni(II), Cu(II) and Cd(II) complexes with orotic acid
and 1,10-phenanthroline (Fig. 1) are reported.
3
Fig. 1 Structures of the ligands: H Or=orotic acid;
phen=1,10-phenanthroline
Experimental
Materials and instrumentation
[
7–11]. The crystal structure determination of the com-
plexes confirms the bidentate coordination of orotic acid
through N(3) and the carboxylate group [12–18]. In the
All chemicals used were analytical reagent products.
Elemental analyses for C, H and N were carried out at
*
Author for correspondence: yesilel@ogu.edu.tr
1
388–6150/$20.00
Akadémiai Kiadó, Budapest, Hungary
Springer, Dordrecht, The Netherlands
©
2006 Akadémiai Kiadó, Budapest

YEŸILEL, ÖLMEZ
Table 1 Analytical data and conductance values of the metal complexes
Found (calc.)/%
N
–1
Yield/
%
2
–1
Complex
Co(H O)
F.W./g mol
Colour
Λ/S cm mol
C
H
[
2
2
(phen)
2
](H
2
Or)
2
·2.25H
2
O
50.79
4.01
13.56
806.09
819.36
806.20
855.07
73
88
87
66
orange
pink
106
105
98
C
34
H
30.5
N
8
O
12.25Co
(50.66) (3.81)
49.50 3.79
(49.84) (3.94)
50.59 3.60
(50.65) (3.75)
48.04 3.95
(47.76) (3.54)
(13.90)
[Ni(H
2
O)
2
(phen)
2
](H
2
Or)
2
·3H
2
O
13.61
C
34
H
32
N
8
O
13Ni
(13.68)
[Cu(H
2
O)
2
(phen)
2
2
](H
2
2
Or)2·2H
2
O
13.63
green-blue
colourless
C
34
H
30
N
8
O
12Cu
(13.90)
[Cd(H
2
O)
2
(phen)
](H
Or)
2
·2H
2
O
12.87
117
C
34
H
30
N
8
O
12Cd
(13.10)
the Tübitak Marmara Research Centre. Magnetic sus-
ceptibility measurements at room temperature were
performed using a Sherwood Scientific MXI model
Gouy magnetic balance. UV-vis spectra were ob-
Results and discussion
Structures of the complexes
Analytical results and the molar conductivity values of
the complexes are listed in Table 1. The complexes
were synthesized in good yields and with high purity.
All complexes were found to be nonhygroscopic and
stable in air. The results of elemental analyses show that
two phen and two aqua ligands have been incorporated
into the M(II) orotates (M=Co(II), Ni(II), Cu(II) and
Cd(II)). The complexes have pseudooctahedral geome-
tries with two phen molecules coordinated to the metal
ions as chelating ligands through their two N atoms and
two aqua ligands in the cis positions. Also the
monoanionic orotate behaves as a counter ion in the
complexes. This result was supported by conductivity
measurements. The molar conductance values (Λ) of the
Co(II), Ni(II), Cu(II) and Cd(II) complexes are 106,
–
3
tained for the aqueous solutions (10 M) of the com-
plexes with a Unicam UV2 spectrometer in the range
of 900–190 nm. IR spectra were recorded in the
–
1
4
000–500 cm region with a Mattson 1000 FTIR
spectrometer using KBr pellets. Thermal analysis
curves (TG, DTG and DTA) were recorded simulta-
neously in a static air atmosphere with a Riga-
ku TG8110 thermal analyser. The heating rate was
–
1
–1
1
0°C min and the DTG sensitivity was 0.05 mg s .
Conductance values were measured on 522 CRISON
conductimeter.
Synthesis of [M(HOr)(H O) ]·H O complexes
2 4 2
A solution of sodium orotate (0.890 g, 5 mmol) in dis-
tilled water (20 mL) was added dropwise with stirring
at 60°C to a solution of MCl ·xH O (5 mmol;
2
–1
1
05, 98 and 117 S cm mol , respectively, indicating
that the complexes are electrolyte in 1:2 ratio in water
and the orotate behaves as a counter ion.
2
2
M=Co(II), 1.185 g; Ni(II), 1.185 g; Cu(II), 0.850 g,
Cd(II), 0.917; x=7, 7, 2 and 0, respectively) in dis-
tilled water (20 mL). The mixture was stirred for 4 h
at 60°C and then cooled to room temperature. The
crystals formed were filtered and washed with 10 mL
of cold distilled water and dried in air.
UV-vis spectra and magnetic moments of the complexes
The λmax and ε values of the various absorption bands,
Δ0 (10 Dq) values of d–d transitions displayed by the
complexes, assignments of d–d transitions and the ef-
fective magnetic moment values of the complexes are
given in Table 2. The Co(II), Ni(II) and Cu(II) com-
plexes exhibit magnetic moment values of 4.27, 2.41
and 1.64 BM which corresponds to three, two and one
unpaired electrons, respectively, which are consistent
with a weak field octahedral geometry as expected.
The Cd(II) complex is diamagnetic.
Synthesis of [M(H O) (phen) ](H Or) ·nH O
2 2 2 2 2 2
(M=Co(II), n=2.25; Ni(II), n=3; Cu(II) and Cd(II), n=2)
A solution of phen (0.792 g, 4 mmol) in ethanol
10 mL) was added dropwise with stirring to a solu-
tion of [M(HOr)(H O) ]·H O (2.0 mmol; M=Co(II),
.605 g; Ni(II), 0.605 g; Cu(II), 0.615 g and Cd(II),
.697 g) in hot distilled water (30 mL). The solutions
(
2
4
2
0
All the complexes comprise broad composite
bands in the UV region. These bands exhibit mainly
three maxima at about 206, 233 and 278 nm, being
due to π→π* and n→π* intraligand transitions of
0
were heated to 60°C in a temperature-controlled bath
and stirred for 4 h. The reaction mixtures were then
cooled to room temperature. The crystals formed
were filtered and washed with 10 mL of cold distilled
water and ethanol and dried in air.
H Or and phen. The assignments of d–d transitions
2
corresponded to an octahedral coordination geometry
of the metal ions and the values of Δ parameter,
0
Racah parameter (B’) and nephelauxetic ratio
212
J. Therm. Anal. Cal., 86, 2006

SPECTROTHERMAL STUDIES OF 1,10-PHENANTHROLINE COMPLEXES
Table 2 Electronic spectra and magnetic moments of the metal complexes
–1
–1
–1
Assignment of
d–d transitions
–1
Complex
λ
max/cm
ε/L cm mol
Δ
0
/cm
μeff/BM
4
4
(
23717)*
21142
1236
–
T
1g→ A2g
4
4
[
Co(H
2
O)
2
(phen)
2
](H
2
Or)
2
·2.25H
2
O
42
18
T → T (P)
T
12481
12853
4.27
1g
1g
4
4
1
1g→ T2g
3
3
3
3
(
29771)*
19157
2853
–
A
2g→ 3T1g(P)
[
Ni(H
2
O)
2
(phen)
2
](H
2
Or)
2
·3H
2
O
15
10
A → T
2.41
2
g
1g
3
1
A
2g→ T2g
2
2
[
[
Cu(H
2
2
O)
2
2
(phen)
(phen)
2
2
](H
2
Or)
2
2
·2H
·2H
2
O
O
14570
–
48
–
E
g
→ T2g
14570
–
1.64
Dia.
Cd(H
O)
](H
2
Or)
2
–
*
calculated
(
B’/B=β) values for the Co(II) and Ni(II) complexes
The UV-vis spectrum for the complex
[Cu(H O) (phen) ](H Or) ·2H O exhibits a very
were found using Tanabe–Sugano diagrams [22]. The
λmax values of the first two absorption bands in the
spectra of [Co(H O) (phen) ](H Or) ·2.25H O are
2
2
2
2
2
2
–
1
broad d–d absorption transition centred at 14570 cm
–
1
–1
(ε=48 L mol cm ). This value was assigned to the
2
2
2
2
2
2
–
1
–1
–1
2
2
1
1236 (ε=18 L mol cm ) and 21142 cm
Eg→ T2g transition, thereby suggesting octahedral
–
1
–1
(
ε=42 L mol cm ). These values were assigned to
geometry around Cu(II). The Δ value for the Cu(II)
0
4
4
–1
complex was obtained as 14570 cm .
the following d–d transitions, ν : T → T and ν2:
1
1g
2g
4
4
4
4
T → T (P), respectively. ν : T → A transition
The colourless Cd(II) complex does not show the
1
g
1g
3
1g
2g
was not observed which is of high energy and shifts to
the UV region and hidden under the intraligand tran-
sitions in the spectrum. The B’, ν and Δ values for
d–d bands as expected.
3
0
IR spectra
the cobalt complex were found as 744, 23717 and
–
2481 cm , respectively. The nephelauxetic ratio
1
1
The main IR group frequencies of the metal complexes
are presented in Table 3. νOH stretching of the coordi-
nated and crystal water molecules appears in the range
–
1
(
B’/B=β) was calculated as 0.77 by using 971 cm for
the free Co(II) ion.
The UV-vis
Ni(H O) (phen) ](H Or) ·3H O exhibits two weak
–1
spectrum
for
of 3371–3603 cm . The coordinated water appears at
[
frequencies lower than those of the crystal water [23].
2
2
2
2
2
2
–1
d–d absorption transitions centred at 12853
–
The N H stretching band at 3160 cm of orotic acid
(3)
1
–1
cm ) and 19157 cm
–1
(
ε=10
L
mol
[7] was clearly observable as strong at 3151, 3155,
–1
3149 and 3161 cm in the IR spectrum of the Co(II),
–
1
–1
(
ε=15 L mol cm ) which support the octahedral ge-
3
3
ometry. These values were assigned to ν : A → T ,
Ni(II), Cu(II), Cd(II) complexes, respectively.
1
2g
2g
3
3
and ν :
A → T , respectively. The ν :
The IR spectra of the all complexes resemble
each other and show the characteristic ν C= O acid +ν C(2) =O
and ν C(6) O +ν C= C absorption bands of the H O moiety.
The stretching modes of the carbonyl groups are used
most frequently for structural studies of various
orotates [7, 17, 18]. Strong absorption bands in the
2
2g
1g
3
3
3
A → T (P) transition was not observed, which is of
2
g
1g
high energy and shifts to the UV region and over-
lapped by the intraligand transitions in the spectrum.
The B’, ν and Δ values for the nickel complex were
2
r
3
0
–
1
found as 691, 29771 and 12853 cm , respectively.
–
1
The nephelauxetic ratio (B’/B=β) was calculated as
0
range of 1620–1705 cm characterize the C=O group
–
.67 by using 1030 cm for the free Ni(II) ion.
1
of the H Or moiety in the complexes. The carbonyl
2
–
1
groups appear as two main peaks at 1709 cm
Table 3 IR spectra of the metal complexes
Complex
νOH
νN(3)H
νN(1)H
020 m
νOHacid
νC=O acid +νC(2)=O
νC(6)=O +νC=C
3
Orotic acid
3524 s
3160 s
2500 w,b
1709 vs
1671 vs
1640 s
2835 m
3
603 m
[
Co(H
2
O)
2
(phen)
2
](H
2
Or)
2
·2.25H
2
O
3151 s
3090 m
–
1707 vs
3
396 s
[
Ni(H
2
O)
2
(phen)
2
](H
2
Or)
2
·3H
2
O
3380 s
3371 s
3155 s
3149 s
3088 m
3050 m
–
–
1703 vs
1703 vs
1622 s
1625 s
[Cu(H
2
2
O)
2
2
(phen)
(phen)
2
2
](H
2
Or)
2
2
·2H
·2H
2
O
O
3
598 m
394 s
[Cd(H
O)
](H
2
Or)
2
3161 s
3060 m
–
1705 vs
1639 vs
3
a
Abbreviations: m – medium, w – weak, s – strong, vs – very strong, b – broad
J. Therm. Anal. Cal., 86, 2006
213

YEŸILEL, ÖLMEZ
–
1
[
ν C= O acid +ν C(2) =O ] and 1671 cm [ν C(6) O +ν C= C ] in the
Thermal
decomposition
of
free H Or [7]. The carbonyl stretching modes in the
[Co(H O) (phen) ](H Or) ·2.25H O proceeds in four
2 2 2 2 2
3
2
Co(II), Ni(II), Cu(II) and Cd(II) complexes were ob-
stages (Fig. 2). The broad endothermic peak
(DTGmax=166°C), in the temperature range of
37–188°C, corresponds to the loss of 2 moles of coor-
dinated water and 2.25 moles of crystallization water
(found 10.43, calcd. 9.49%). The anhydrous Co(II)
complex is stable up to 235°C. The second and third
stages, in the temperature range of 235–410°C, are re-
lated to the consecutive decomposition of phen and
the decarboxylate of orotate, respectively. During
these stages, the Co(II) complex releases one phen
–
served at 1704, 1620 cm ; 1703, 1625 cm ; 1703,
1
–1
–
1
–1
625 cm and 1705, 1639 cm , respectively. The
1
–
1
νOH(acid) vibration bands which appeared at 2500 cm
in the free orotic acid have not been observed in the
all complexes. The disappearance of the bands was at-
tributed to the deprotonation.
–
1
The ν C(4) –C(5) was observed at 1312 cm , which
–
1
appears as a main peak at 1295 cm in the free H Or
3
[
7], in the [Co(H O) (phen) ](H Or) ·2.25H O com-
2 2 2 2 2 2
plex whose crystal structure has been determined
24]. In this complex, monoanionic orotate behaves as
a counter ion. The ν C(4) –C(5) of the Ni(II), Cu(II) and
Cd(II) complexes, appeared at 1310, 1337 and
and two CO molecules (found 32.91, calcd. 33.27%).
2
[
This type of behaviour of neutral ligands in the
saccharinato [26, 27], salicylato [28], isoorotato and
2-thioisoorotato [29] complexes has been reported
earlier. The exothermic and endothermic effects at
about 264 and 377°C, respectively, are likely due to
–
1
1
335 cm , respectively. As a result, the IR spectrum
of the complexes indicates that the orotic acid is
monoanionic and counter ion as supported by X-ray
24, 25] and conductivity measurements.
the release of phen and CO . The IR spectra of the
2
[
Co(II) complex heated just to the end of this mass loss
show no evidence of CO bands. In the last stage, the
2
strong exothermic peak (DTGmax: 452°C) is associ-
ated with the burning of organic residue, leading fi-
Thermal analysis
The thermal analysis curves of the studied complexes
are shown in Figs 2–5.
nally to the Co O . The endothermic peak at 905°C is
3 4
related to the conversion of Co
O to CoO. The over-
4
3
Fig. 2 TG, DTG and DTA curves of
Fig. 4 TG, DTG and DTA curves of
[
Co(H
2
O)
2
(phen)
2
](H
2
Or)
2
·2.25H
2
O
2 2 2 2 2 2
[Cu(H O) (phen) ](H Or) ·2H O
Fig. 3 TG, DTG and DTA curves of
Ni(H O) (phen) ](H Or) ·3H
Fig. 5 TG, DTG and DTA curves of
2
[Cd(H O) (phen) ](H Or) ·2H O
[
2
2
2
2
2
2
O
2
2
2
2
2
214
J. Therm. Anal. Cal., 86, 2006

SPECTROTHERMAL STUDIES OF 1,10-PHENANTHROLINE COMPLEXES
all mass loss (found 91.87, calcd. 90.71%) agrees
with the proposed structure well.
The thermal analysis curves of the
Ni(H O) (phen) ](H Or) ·3H O complex (Fig. 3) is
strong exothermic peak is associated with the burn-
ing of the organic residue in the range of 478–576°C.
The final decomposition product, namely CdO was
identified by IR spectroscopy with corresponding
spectra obtained under the same conditions as the
pure oxides. The total mass loss is found as 86.18%
(calcd. 84.18%).
[
2
2
2
2
2
2
similar with the Co(II) compound (Fig. 2). The com-
plex mainly exhibits four stages of decomposition.
In the stage of range 43–184°C, involves endother-
mic decomposition at 74, 145 and 179°C (DTG) cor-
responding to the loss of five moles of water mole-
cules as indicated by TG mass loss (found 11.09,
calcd. 10.93%). In the second and third stages, the
successive decomposition process is initially exo-
thermic, an endothermic contribution is also ob-
served in the DTA curve of the complex. In these
stages of the complex, one mole of phen and two
Based on the initial DTGmax temperatures, the ther-
mal stabilities of the complexes follow the sequence:
Cd(II), 68°C<Ni(II), 74°C<Cu(II), 135°C<Co(II), 166°C.
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2
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the fourth stage, remaining organic part is abruptly
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3 I. Ucar, A. Bulut, O. Z. Yesilel, H. Ölmez and
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4 T. Solin, K. Matsumoto and K. Fuwa, Bull. Chem. Soc. Jpn.,
(
found 9.89, calcd. 10.92%). The isoorotic acid and
-thioisoorotic acid-metal complexes and their am-
monium, sodium and barium salts decompose by re-
2
54 (1981) 3731.
leasing of CO [29, 30]. The last strong exothermic
2
15 T. S. Khodashova, M. A. Porai-Koshits, N. K. Davidenko
and N. N. Vlasova, Koord. Khim., 10 (1984) 262.
stage can be assigned to the combustion of the resid-
ual organic matter. The final solid product of thermal
decomposition was identified as CuO (found 89.07,
calcd. 90.13%).
16 A. Karipides and B. Thomas, Acta Cryst., C42 (1986) 1705.
1
7 H. Icbudak, H. Ölmez, O. Z. Yesilel, F. Arslan, P. Naumov,
G. Jovanovski, A. R. Ibrahim, A. Usman, H. K. Fun,
S. Chantrapromma and S. W. Ng, J. Mol. Struct.,
The [Cd(H O) (phen) ](H Or) ·2H O complex
2 2 2 2 2 2
6
57 (2003) 255.
8 H. Olmez, H. Icbudak, O. Z. Yesilel, C. ArÏcÏ and
D. Ülkü, Z. Kristallogr., 219 (2004) 300.
is decomposed at three stages (Fig. 5). The thermal
dehydration of the complex occurs by giving endo-
thermic effects at 68 and 124°C (DTGmax). The TG
curve of the complex shows a mass loss in the range
of 56–143°C corresponding to the loss of two moles
of coordinated water and two moles of crystal water
1
19 M. J. Plater, M. R. J. Foreman, J. M. S. Skakle and
R. A. Howie, Inorg. Chim. Acta, 332 (2002) 135.
20 I. Mutikainen, Finn. Chem. Lett., (1985) 193.
21 T. T. B. Ha, A. M. Larsonneur-Galibert, P. Castan and
J. Jaud, J. Chem. Crystallogr., 29 (1999) 565.
(
found 9.54, calcd. 8.43%). The second stage is re-
lated to the decomposition of neutral two moles of
phen ligand and two moles of CO . The Cd(II) com-
2
2 D. Sutton, Electrostatic Energy Level Diagrams and the
Spectra of Octahedral Complexes. In Electronic Spectra of
Transition Metal Complexes, McGraw-Hill, London 1968,
p.115.
2
pound shows an exothermic effect at about 445°C
that can be assigned to the phase transition. The
J. Therm. Anal. Cal., 86, 2006
215

YEŸILEL, ÖLMEZ
2
3 K. Nakamoto, Infrared and Raman spectra of Inorganic
29 F. Hueso-Urena and M. N. Moreno-Carretto,
Thermochim. Acta, 182 (1991) 9.
and Co-ordination Compounds, Wiley and Sons,
New York 1986, p. 150.
30 F. Hueso-UreÔa, M. N. Moreno-Carretto and
J. M. Salas-Peregrín, Thermochim. Acta, 170 (1990) 225.
2
4 A. Bulut, H. Icbudak, O. Z. Yesilel, H. Ölmez and
O. Büyükgüngör, Acta Crystallogr., E59 (2003) m736.
5 O. Z. Yesilel, Tesis Doctoral, Turkey 2004.
6 P. Naumov, O. Grup¹e, V. Jordanovska, B. Boyanov and
G. Jovanovski, J. Therm. Anal. Cal., 65 (2001) 871.
7 P. Naumov, V. Jordanovska, B. Boyanov and G. Jovanowski,
J. Therm. Anal. Cal., 66 (2001) 469.
2
2
Received: June 23, 2005
Accepted: December 20, 2005
OnlineFirst: March 20, 2006
2
28 H. Ölmez, F. Arslan and H. Icbudak, J. Therm. Anal. Cal.,
DOI: 10.1007/s10973-005-7137-2
7
6 (2004) 793.
216
J. Therm. Anal. Cal., 86, 2006